Dithio-bis-aziridine and 2-methyl derivative thereof



United States Patent 2 Claims. (Cl. 260-239) (Granted under Title 35,U.S. Code (1052), see. 266) A non-exclusive, irrevocable, royalty-freelicense in the invention herein described throughout the world for allpurposes of the United States Government, with the power to grantsub-licenses for such purposes, is hereby granted to the Government ofthe United States of Amerme.

This application is a division of Serial No. 305,907, filed July 22,1963, now abandoned, which is a division of Serial No. 210,598, filedJuly 17, 1962, which in turn is a continuation-in-part of Serial No.103,176, filed April 14, 1961, now abandoned.

This invention relates to the use of certain synethetic organiccompounds for the control or eradication of insect populations bycausing sexual sterility in the insect.

It has been demonstrated that an insect population may be controlled oreradicated by the introduction of a sufficient quantity of sexuallysterile insects into that population. This method was first used in theelimination of the screw-worm (Callitroga hominovorax, Coq.) from theisland of Curacao and later from Florida and the Southeastern States.Reared flies made sexually sterile by gamma irradiation in the pupalstate released in quantities estimated to be 2 to 4 times greater thanthe wild population caused eradication within 3 months.

The control of an insect population by chemical sterilization of thewild insects has also been reported. Here a bait containing achemosterilant was distributed periodically in an isolated area heavilyinfested with house flies (Musca domestica, Tim). The population wasalmost completely eliminated within one month.

Sterilization of insects in nature by use of gamma irradiation is notpractical and its use on reared insects has been found to be expensive,dangerous, and troublesome. The same eifect can be more easily obtainedby incorporating the proper chemosterilant in a food or bait. Topicalapplication by spray or dip is still another possible means ofadministering the material.

Therefore an object of this invention is to provide a material that willcause the sexual sterility of a wild insect when properly administeredto it.

Another object of this invention is to provide a material which willcause sexual sterility when fed or applied to reared insects and thuseliminate the need for dangerous and expensive ionizing radiation.

In general according to this invention certain sulfur containingderivatives of aziridine have been found to cause sexual sterility whenincorporated in the food of the screw-worm fly, house fly, and theMexican fruit fly (Anestrepha ludens, Loew). These compounds may berepresented by the following structural formulae in which R is eitherhydrogen or an alkyl group.

3,197,455 Patented July 27, 1965 ice Compounds Ia, Ib, Ho, and IIb canbe prepared from thionyl chloride or sulfur monochloride and theappropriate aziridine in an inert solvent in the presence of a tertiaryamine. 1,1'-sulfonylbis [Z-methylaziridine] (III) was prepared byoxidation of 1,1'-sulfinylbis {Z-rnethylaziridine] (lib).

The invention is specifically illustrated in the following examples:

Example 1.Preparati0n of 1,1-sulfinyldiaziridine (Ia) To a solution of51.6 g. (1.20 moles) of ethylenirnine and 106 g. (1.05 moles) oftriethylamine in 500 ml. of dry benzene was added drop-wise 59.6 g.(0.50 mole) of thionyl chloride in 300 ml. of benzene. The reactionmixture was stirred and kept at 5 C. during the addition. After standing20 hours, the precipitate was collected by filtration and filtratedistilled. The yield of 1,1-sulfinyldiaziridine boiling 49-53 C. (0.1mm.) was 32 g.; 1.5130.

1,l' sulfinylbis(Z-methylaziridine) (Ia), also prepared by this methodfrom the corresponding 2-ethylenimine, boiled at 5256 C. (.1 mm.); n1.4854; density 1.0924.

Example 2.-Preparati0n of 1,1'-dizhi0diaziridine (11a) A solution of67.5 g. (0.50 mole) of sulfur monochloride in 200 ml. of dry benzene wasadded drop-wise to a cooled and stirred solution of 47.4 g. (1.10 moles)of ethylenimine and 111 g. (1.10 moles) of triethylamine in 800 ml. ofdry benzene. The temperature was maintained at 5 C. during the additionand at 25 C. for 20 hours. After filtration the solution was distilledto give 44 g. of 1,l-dithiodiaziridine boiling 44-46 C. (0.03 mm); o1.5776.

1,1'-dithiobis(2-methylaziridine) (IIb) also prepared by this methodfrom the corresponding Z-ethylenimine, boiled 52-56 C. (0.2 mm); 121.5368.

Example 3.-Preparati0n of 1,1'-sulf0nylbis(2-methylaziridine) (III) To35 g. (0.22 mole) of 1,1'-sulfinylbis(2-methylaziridine) (IIb) dissolvedin 1 liter of acetone was added 38 g. of finely ground potassiumpermanganate in 4 g. portions. The permanganate color was not dischargedafter the last addition and the precipitated manganese dioxide wasremoved by filtration. Vacuum distillation Example 4 These compoundswere tested against the house fly, Mexican fruit fly, and screw-worm inthe following procedures:

The normal food for rearing house flies was made up ;of six parts ofsugar, six parts of nonfat dry-milk, and one part powdered egg. Thecandidate chemosterilant was incorporated in this mixture and fed tonewly emerged flies. After seven days Chemical Specialties ManufacturersAssociation standard medium was placed in the cage for oviposition andinspected daily or until the flies were dead. Viability of the eggs wasdetermined by inspection of the medium two days after oviposition forgrowing larvae.

The Mexican fruit fly was fed a mixture of three parts of granulatedsugar, and one part orange juice crystals and some protein hydrolyzatein a separate container. This food combined with the test compound wasprovided to the fruit flies from the day of adult emergence. The flieswere egged a few days after sexual maturity and twice thereafter atweekly intervals using oviposition shells placed in the cages for twohours late in the morning. The eggs were counted, incubated on blottingpaper, and the emerging larvae counted to determine hatch.

Screw-worm flies less than 24 hours old were fed a mixture of thechemosterilant fixed with honey. Freshly prepared food was oifered dailyfor eight days when the females were removed to. oviposit. Females wereplaced in small vials with a small quantity of ground beef as an oviposition medium. After oviposition was completed the eggs weretransferred to damp paper and incubated for 24 hours to determineviability.

,The following results were obtained:

Percent hatch Serew- House Mexican worm fly fly fruit fly Feeding level1% 1% 2% Compound:

1,1-Sulfinyldiaziridine No eggs 0 1, l-SulfinylbisIZ-rnethylaziridine] 212 8 1,1 -Sullonylbls['Lmethylaziridine]. 1 0 toxic toxic1,1-Dithi0diaziridine 0 100 1,1-Dithiobis[2-mathylaziridine] toxic 10.5% feeding level.

References Cited in the file of this patent 'UNITED STATES PATENTS2,917,492 12/59 Reeves et al. 260-239 2,943,976 7/60 Goodhue et al.16733 3,006,912 10/61 Vierling et al. 260-239 3,012,935 12/61 Goodhue16733 3,014,902 12/61 Nakabayashi 260239 NICHOLAS s. RIZZO, PrimaryExaminer.

1. 1,1''-DITHIODIAZIRIDINE.
 2. 1,1''-DITHIOBIS(2-METHYLAZIRIDINE).